Application of visbreaker analysis tools to optimize performance

ABSTRACT

A system and method for quantifying opaque inhomogeneities within a fluid sample. The system uses an optical lens system to focus a light beam onto a stage where the sample is introduced. The light beam is directed onto the sample in a pattern such that the intensity of transmitted light is measured as a function of path length. A photo detector measures the transmitted light through the sample. Fluctuations in transmitted light intensity are then correlated with detection of opaque inclusions in the sample. The system also includes an automated program which utilizes these optical concentration measurements to determine the fouling potential of visbroken tars, and regulates the introduction of chemical inhibitors into a visbreaker unit to improve the yield of light streams and/or economic value of product.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/178,846 filed Jul. 11, 2005.

FIELD OF THE INVENTION

The present invention relates to systems and methods for characterizingand quantifying a dispersive medium; specifically, measuring theconcentration of particles or the tendency toward forming a dispersedphase within a fluid sample. The present invention also provides aprogram which uses these measurements of concentration to monitor andcontrol operation of a visbreaker unit to improve the yield of lightstreams.

BACKGROUND OF THE INVENTION

Thermal conversion is a process in which, by the application of heat,large hydrocarbon molecules are broken into smaller molecules with alower boiling point. These operations are carried out in the industry ofcrude oil refining by plants such as a visbreaker, coker, andhydrocracker for obtaining intermediate or light cuts of higher value,from heavy residues of lower commercial value. The thermal crackingapplied in the visbreaker process will also reduce the viscosity andpour point of the heavy residues.

It is well known that the fouling potential of a fluid can be estimatedand characterized by the concentration of the dispersed phase,particularly by the concentration of the dispersed phase present in aspecific size range. In hydrocarbon systems in particular, it has beenrecognized that the concentration of asphaltenes (i.e., carbon particlesor opaque species) with linear dimension greater than about 2 microns invisbroken tars is a good indication of the fouling potential of thematerial.

The VSB process was developed some years ago with the intention ofobtaining a viscosity decrease in heavy products in order to reduce theamount of higher valued flux to meet the viscosity specification of thefinished heavy fuel product. Today, however, it is managed withsubstantially different objects, namely with the aim of obtaining amaximum transformation into middle and light distillates to meet themarket requirements.

The controlling factor in obtaining a high conversion is the need toobtain a stable residue. In fact an increase of the cracking temperaturecertainly would involve a higher conversion in light and middledistillates, but it would produce a much more instable tar which wouldproduce a final product outside the required stability specifications.

An increase of the light streams is achieved by increasing the crackingseverity through an increase of the outlet furnace temperature of theVisbreaker furnace. While increasing this temperature arbitrarily willserve to drive the conversion rate higher, it also comes at the cost ofproducing a highly unstable tar as a precipitate in the process, with ahigh concentration of asphaltene particulates. This particulate matterconstitutes a severe fouling threat to the energy recovery devices (i.e.furnace and heat exchangers) in the process. As such, in order tomaximize the profitability a Visbreaker unit, it is desirable tooptimize the outlet furnace temperature while maintaining the stabilityof the produced tar. While it is known that high temperature dispersantsand anti-foulants can be introduced into the system to reduce thetendancy and rate of fouling, prior art systems have not been entirelysatisfactory in providing an automated system for determining an optimumtype and/or quantity of chemical dispersants and anti-foulants to beintroduced into the visbreaker unit in order to maximize plantprofitability. The present teachings will show that if the foulingpotential of the tar can be quantified, then the precise level ofchemical inhibitor can be dosed to maximize the plant profitability.

Therefore, in one aspect the present invention provides a simplified,automated system and method that can easily be used to carry out opticalanalysis of visbroken tars and other fluid samples in order tocharacterize and quantify the concentration of particles within thefluid sample with high accuracy and reproducibility. In another aspect,the present invention utilizes these concentration measurements todetermine the fouling potential of the visbroken tars, and regulates theintroduction of chemical inhibitors into the visbreaker unit to improvethe yield of light streams. In yet another or further aspect, a sequenceof aliquots are prepared from the same sample at different dilutions todrive phase separation, producing a sequence of concentrationmeasurements correlated to a classical measurement of peptization value(PV), a qualitative measure of the product quality. These and otheraspects of the present invention will become apparent to those skilledin the art upon review of the following disclosure.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a system and method forestimating a concentration of inhomogeneities contained within a tarbyproduct of visbreaker operations. The invention does so by measuringthe modulation of transmitted light through a fluid sample. The systemuses a strongly convergent optical lens system to focus light onto aprepared sample. In one exemplary embodiment, the optics of aconventional optical microscope are used. A 3-dimensional translationstage is installed downstream of the focusing optics so that the samplecan be scanned over a large region, and at a specific focal plane. Aphoto detector is placed on the opposite side of the stage from thefocusing optics to measure the transmitted light through the sample. Thephotodetector is read-out by an analog-to-digital converter (ADC) inorder to provide a digital (i.e., quantitative) measure of thetransmitted light intensity. The translation stages are then moved in apattern, such that the intensity of the transmitted light is measuredover a representative path across the sample. When an opacity, scattereror opaque particle of a threshold size is encountered in the sample, theintensity of the transmitted light is strongly attenuated. Such changeof light intensity is then correlated with the detection of an opaqueparticle in order to characterize and quantify the concentration ofparticles within the fluid sample with high accuracy andreproducibility. Data processing algorithms are implemented to determinethe background noise level associated with the acquired data and to seta threshold level. As such, a specific signal-to-noise ratio can bespecified to define when a detection event is registered. Sizediscrimination may be achieved according to the physical dimensions ofthe beam waist of the focused light beam.

In another aspect, the present invention utilizes the concentrationmeasurement data to estimate the fouling potential of visbroken tars ina visbreaker unit in order to regulate introduction of chemicalinhibitors into the visbreaker unit and improve the yield of lightstreams. The invention provides an automated program which allows theuser to maximize the production of light streams by modeling thecorrelation between operational parameters such as feed quality,cracking severity, conversion rate, run length, and fouling rate of thesubject exchanger or furnace in order to regulate introduction ofchemical inhibitors into the visbreaker unit in accordance with customerspecifications and/or production requirements.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view of the scanning apparatus of the present invention,showing the schematic relationship of the various elements;

FIG. 2 illustrates an example of a computer screen displaying a dataacquisition interface in accordance with the present invention;

FIG. 3 is a diagram illustrating optics used to convergently focus alight beam to a narrow beam waist;

FIG. 4 illustrates a plurality of spaced apart linear scans comparedwith a solid block representing an equivalent effective surface area;

FIG. 5 is a graph illustrating raw light transmission data obtained overa single line scan;

FIG. 6 is a graph illustrating the raw data of FIG. 5 after the data hasbeen filtered to remove line noise and gross intensity variations;

FIG. 7 is a graph illustrating decreasing statistical error as afunction of overall scan length;

FIG. 8 is a graph showing the correlation of sample inhomogeneity, asmeasured by the instrument to samples with a varying degree of dilutionfrom a fully cracked (i.e., high asphaltene particle density) sample;

FIG. 9 is a schematic of the mechanics of the chemical effect of thedispersants;

FIG. 10 is a graph of the relation of PV to the Furnace OutletTemperature (FOT) with and without chemical treatment;

FIG. 11 illustrates tar stability and conversion as asphaltenes aredisbursed in the continuous phase through the peptizing action ofaromatics and resins;

FIG. 12 is a graph illustrating raw data obtained from a visbreakerconversion trial;

FIGS. 13-16 are graphs illustrating raw data obtained from a conversionenhancement application;

FIG. 17 is a graph illustrating VFM data versus corr. skin temperature;

FIG. 18 is a schematic diagram illustrating exemplary visbreaker processtypes; and

FIGS. 19A, 19B illustrate Pv measurement with a measurement system ofthe present invention.

DETAILED DESCRIPTION OF THE INVENTION

Exemplary embodiments and examples describing the present invention willbe described below with reference to the accompanying drawings. As shownin FIG. 1, this invention uses an optical system as generally indicatedby the number 10, which in the present exemplary embodiment comprises aconvergent lens, a light source 12, and a multi-axis translation stage14. The light source 12 may be implemented, for example, in the form ofa solid state visible laser. An infra-red (IR) laser may also be used,and is in some cases preferable owing to the fact that HC solutions aretypically much more transparent to IR light, than visible light. Thetranslation stage 14 may be moved horizontally in the x and y directionsin response to control signals generated by an associated computer 20 todirect the light beam along a plurality of paths through the sample. Thethird axis moves the stage vertically, towards and away from thefocusing lens. This permits selection of a focal plane within thesample. In another exemplary embodiment, the present inventioncontemplates providing means for moving the light source 12 with respectto the sample, thereby allowing the light beam to be directed throughthe sample to achieve the same results. Moreover, the present inventionalso contemplates usage of a flow cell to receive a flow of samplefluid, wherein the sample fluid flows through the flow cell while thelight beam is directed through a portion of the flowing sample. Alsoimplemented is a photodetector 16, for example, a PIN photodiode,located on the opposite side of the stage 14 to detect light 13 beingtransmitted through the sample volume, which is located on thetranslation stage. The photodetector 16, in turn, is connected by aconnector and cable 17, for example, a twisted pair with BNC connector,to an analog-to-digital (A/D) converter 18 to quantify the transmittedlight intensity. As described below, this is done to sample or detectthe occurrence of inhomogeneities in light transmission which may becaused by mineral and other inclusions, and agglomerating or stablelocalized dark matter of various types.

In one exemplary embodiment of the invention, a colloidal fluid samplematerial of thick viscous tar sampled from a Visbreaker is placed on thetranslation stage 14. Depending on the conditions in the Visbreakerunit, the sample may or may not contain asphaltene (or carbon based)particles. The asphaltene particles within the tar medium are opaque tovisible light. The tar medium is also opaque to visible light when thepath length through the medium typically exceeds a linear dimension ofabout 1 cm. A sample volume is dispensed on a slide, or flow cell 15such that a typical sample thickness of 10-20 microns is produced. Assuch, the thickness of sample medium should be made thin enough so as toprovide a differential transparency between the viscous tar medium andthe asphaltene particles in question. In this exemplary embodiment, inorder to optimize light transmission from a low power light source, asolid state laser that produces radiation at about 633 nm is chosen.This provides adequate power at a suitable region in the EM(electromagnetic) spectrum to provide transmission through a thin layerof tar, while the carbide particles remain opaque.

In order to have sensitivity to the specific sized inhomogeneities,appropriate optics should be used to focus the laser light onto thesample. The choice of a monochromatic light source allows the design ofthe optics to be optimized. As shown in FIG. 3, a highly convergent lenssystem 200 is used to focus the light beam 100 down to a beam waist ofapproximately 1 micron. The size of the beam waist determines theminimum cross-dimension an inhomogeneity must have to fully attenuatethe laser light. If an inhomogeneity is smaller than 1 micron, it willstill allow the transmission of light. As such, the focusing opticsdefine, in part, a threshold size for inhomogeneity detection. Anequation for calculating the beam waist is as follows:W=0.61λ/d

Where

-   -   W=beam waist (1/e) width    -   λ=wavelength of light    -   d=numerical aperture

For example, if λ=633 nm and d=0.56, then W=0.7 μm.

Since we are interested in inhomogeneities larger than 1 micron (andsmaller than ˜20 microns), we do not use an IR laser, even though the HCsolutions are more transparent to IR radiation because the beam waistwould increase in size for the given optics. As such, we would reducethe sensitivity of the instrument. Preferably, the wavelength and beamwaist are also chosen to minimize interference artifacts that may ariseas the concentration of dispersed phase increases or the samplethickness varies (e.g., under a cover slide.)

The fluid sample 120 thickness is chosen to be about 10 microns. Thebeam 100 is focused on the slide 104, below a cover slip 102, or a flowcell in the sample volume. The depth and width of focus are constrainedby the optical system and the selected light wavelength. In oneexemplary embodiment, both dimensions are selected to be approximately 1micron.

FIG. 2 illustrates an example of a screen display presented by thesoftware of the present invention. The screen display illustrated inFIG. 2 represents a data acquisition interface allowing the operator tospecify a variety of scanning acquisition, analysis parameters,operating conditions of the instrument, and results of the measurement.The methods by which the operator selects items, inputs data, andotherwise interacts with the data acquisition interface areconventional, and further discussions of these operations are notprovided herein. In an exemplary embodiment of the invention, dataacquisition software was implemented via Visual Basic® in Excel® withanalysis and signal processing code being implemented in GNU Octave,although those skilled in the art of software programming willappreciate that many other software programming means may be used toachieve the same results.

A testing plan was designed and implemented to validate and measure thescanning performance of an exemplary embodiment of the presentinvention. In particular, measurement repeatability is validated byanalyzing the variation between identical measurements. Reproducibilityof the data is examined by analyzing the effects of scanning differentregions in the sample. This is complicated by the effects of sampleinhomogeneity. Accuracy of the system is tested by comparing thescanning data with visual images and PV (PV=peptization value) of thesample. Precision of results is analyzed for statistical uncertaintywith path length and by optimizing sample area, as discussed in moredetail below.

FIG. 4 illustrates an example of how the scanning system samples a largeregion of the sample. The array of linear scans (shown on the right sideof FIG. 4) represent the same effective surface area as the small boxillustrated on the left side of FIG. 4. For example, an array of 20linear scans of 15 mm length with a 1 micron wide laser beam effectivelysamples the same area as does the smaller 0.48 mm×0.64 mm box. However,by arranging the sampling path to extend over a larger region of thesample, the effects of sample inhomogeneity, local fluctuations in thesample, and sample variation are reduced drastically. As such, thestatistical results are much more accurate and reproducible.

To demonstrate the repeatability of our scanning results, five identical15 mm scans from a same sample, each covering a 0.015 mm² effective areawere measured. The measurement showed that the number of counts per 15mm line scan were identical within 95% confidence limits. Increasing thesampling region to 20-15 mm scan paths, the same systematic effects wereseen. After applying statistical analysis to the results, it wasobserved that the single line scan measurements are normallydistributed, with a standard deviation (σ)=1.6 counts on a mean of 8.0counts. Furthermore, the total integral count of the sample was 159 witha standard deviation of 9 counts. This shows that both the meaninhomogeneity count per path, and the total integral inhomogeneity countwere statistically identical and repeatable, over the separate trials,thus demonstrating that instrument stability and repeatability isexcellent. It also demonstrates that the fractional error can be reducedby increasing the sampling length. This is due to the fact thatindependent errors do not add linearly, but in quadrature.

As can be noted from the above data, the system of the present inventionis capable of minimizing and quantifying the effects of sampleinhomogeneity.

Turning now to FIG. 5, there is shown a graph representing exemplary rawdata obtained from a single line scan of 15 mm length taken during a 10second acquisition window.

In FIG. 6, the raw data of FIG. 5 is processed by a Fourier filtering toremove 50/60 Hz line noise and a median filter is used to remove grossintensity variations to extract the number of counts above a thresholdvalue. This process may be repeated for all line scans (e.g., 20 linescans) to calculate the total homogeneity areal density of the sampleunder test. In one example, the number of peak counts from a single linescan is calculated asρ₁=(9±3)÷(15 mm×1 μm)=600±200 mm⁻²

Repeating this calculation for a measurement spanning over 20 paths, theerror decreases as shown below:ρ_(tot)=(149±12)÷(20×15 mm×1 μm)=497±40 mm⁻²We see that the error decreases according to Gaussian statistics wherethe error propagates in quadrature which is a well known statisticalproperty.

As shown in FIG. 7, an approximate 5% uncertainty is achieved at 10 linescans of 15 mm length (i.e., 0.15 mm² effective area). Statistical erroris thus shown to decrease with N^(−0.6), where N is the number of 15 mmpath length multiples. From the exemplary data of FIG. 7, it is shownthat an overall path length of about 150 mm (10×15 mm) would achieve anapproximate 5% error.

In order to determine the background noise in the signal as in FIGS. 5and 6, the present invention provides a software algorithm, whichautomatically computes the background noise and sets a discriminatorlevel or threshold for registering a sample inhomogeneity. A measurementof the light transmission is made when no scanning is occurring. Thus,the signal is an estimate of the nominal noise. Calculating the standarddeviation of this signal distribution allows the estimate. The value canbe used to determine a fixed signal-to-noise ratio on which to acceptinhomogeneities.

In accordance with the present invention, the instrument is capable ofquantifying the inhomogeneity of a solution in an automated and timelyfashion.

To demonstrate the capabilities of the present invention, the followingsample specimens, with various concentrations of asphaltenes were usedfor analysis and validation:

-   -   Specimen A: 9630 Asls, PV=1.7, low particulate density (highly        diluted).    -   Specimen B: 9630-6, PV=1.4, intermediate particulate density        (partially diluted).    -   Specimen C: 9630-7, PV<1.0, high particulate density, heavily        cracked sample (slightly diluted).    -   Specimen D: 9630-mod, 13% 9630-7+9630 Asls, PV=about 1.35        (partially diluted).

The scanning results from these samples were then compared tophotographs of the samples, and a correlation was found between theimages and the scanned results. A graph showing the correlation ofparticle density as measured by the instrument to samples with a varyingdegree of dilution from a fully cracked (i.e., high asphaltene density)is shown in FIG. 8.

Overall, the testing results demonstrate that the system of the presentinvention provides good repeatability and shows correlation with visualimage views. It has been shown that a relatively large sample area maybe covered with automated operation, thus reducing the effects of localfluctuations in inhomogeneity density. Data can also be assigned anerror to quantify precision of results.

We also disclose a program to monitor and control the operation of aVisbreaker unit in a hydrocarbon processing facility (refinery). Theprogram allows the user to maximize the production of light streams(i.e., usually diesel) while maintaining a highly stable residual tarand reducing the chance that rundown of the tar will foul the preheatheat exchangers.

It is known that the stability of residual visbroken tar and its foulingpotential can be measured by the peptization value (PV) and the hotfilterable solids (HFT). Note that HFT and PV are two different metricsas HFT is a product specification whereas PV is a characterization ofthe visbroken tars towards the asphaltene precipitation potential. Theoptical measurement device (referred to hereinafter as ‘VFM’) of thepresent invention measures a quantity which is a measure of the opaquefilterable solids within a tar sample. The automated program of thepresent invention utilizes the VFM concentration measurement data toestimate the fouling potential of the visbroken tars. This estimate inturn is used to gauge the needs for optimum feed of chemical treatments.

It is known that high temperature dispersants and anti-foulants are themain components in a chemical regiment used to treat Visbreakers. Thereare specific chemical families that are particularly effective for usein the Visbreaker for reducing fouling of heat exchanging surfaces (i.e.exchanger, furnace, etc.) and subsequently stabilizing the producedvisbroken tar. The program of the present invention is configured toselect the type and quantity of chemistry required to satisfy productionrequirements. Specific chemical entities include, but are not limited topolyisobutenylphosphonic acids and esters, polyisobutenylthiophosphonicacids and esters, alkylphosphonate phenate sulfides and disulfides thatmay be neutralized with alkaline earth metals or amines polyisobutenylsuccinimides, polyisobutenylsuccinate alkyl esters, magnesium or calciumsalts of alkyl or dialkylnaphthelene sulfonic acids as described in U.S.Pat. No. 4,927,519 and EP Patent No. 321424B1.

These antifoulant materials have been found to function at low dosages,1-200 ppm, to prevent the undesirable deposition or fouling of surfacesin visbreakers, as well as prevent the carboneceous deposition invisbroken heavy oil products (tar). Fouling in heat exchangers is mostgenerally thought to occur by first generating an unstabilizedmacromolecular particle that is no longer dissolved in the fluid, or isno longer a stable colloidal species. This occurs due to the thermalstress on the hydrocarbon. Initial deposition occurs, and furtherdestabilized species adsorb onto the site of original deposition. Biggerparticles in the hydrocarbon will be more prone to contact and coalesceto the surface. Dehydrogenation of the adsorbed hydrocarbon will bedriven by heat and make the deposit more tenacious as crosslinkingreactions occur.

The dispersants are generally understood to function by a variety ofmechanisms. First, the dispersant materials adsorb to the surfaces ofgrowing insoluble particles and act to keep these particles small;typically less than 1 micron. Thus, the particles are more prone tocontinue to flow through the system and not settle on heat exchanger orother surfaces. This can be described by Stokes law, which is dependenton the radius of the particles. This is schematically shown in FIG. 9.The dispersants act by a combination of steric stabilization, which actsto repel approaching particles (dramatically increase entropy of localsystem and drive solvent in between particals), and blocking of polarsites on the particles which act as a driving force for coalescence.Light scattering evidence exists that shows that dispersant treatedthermally stressed fluids generate particles that are up to two ordersof magnitude smaller than untreated hydrocarbon fluids.

Even if the particles are not small, the above mechanism explains howthe particles will be less prone to coalesce to other particles insolution, or to material already deposited on the surface.

It has also been shown that the nature of the surface plays a role inthe ability of thermally stressed fluids to deposit. Metal surfaces withhiger roughness, edges, or polarity are more prone to fouling. Thesedispersants will adsorb to such surfaces and discourage particulate oramorphous insoluble hydrocarbon from sticking to the surface.

The reaction of hydrocarbons at elevated temperatures with oxygen (evenvery low levels such as <5 ppm) will result in formation of polarfunctionalities that can drive coalescence of particulate, as well asaccelerate the dehydrogenation of adsorbed hydrocarbon, which makes itsremoval from the surface by turbulent flow much less likely. Dispersantadsorption will block the mass transfer of the oxygen to the surface,and some of these described anti-foulants have antioxidant abilities byinterfering with radical reactions.

In addition, the visbroken tar is generally believed to be colloidal innature, with more highly polar and higher molecular weight asphaltenespecies being stabilized in the fluid by smaller resin molecules. As thethermal stress disturbs the relationship of the adsorbed resins toasphaltenes, and by driving the conversion of resins to asphaltenes, andby making the asphaltenes more polar, these systems can be described asbeing more “unstable” or prone to deposition. The dispersants describedhere are believed to replace the disturbed or destroyed resins andre-stabilize the asphaltene system.

As described herein, the VFM measurement data gives information on thesolids content in the residue (tar). Higher amounts of solids will givea higher precipitation potential. The solids might be introduced intothe system by the feed (poor feed quality) and/or through the crackingprocess. The higher the cracking severity the higher the solids contentin the residue likely will be.

Based on defining a baseline, which is unit dependent, the VFM dataprovides information in increasing response to decreasing solids contentin the tar. Depending on the main cause of the solids increase (feed orcracking severity) the device can help to optimize the chemicalinjection rate (if solids are from feed or severity want to bemaintained) in order to maintain the fouling rate and thus keeping unitrun-length under control. If solids increase is due to cracking severityonly, the VFM measurement provides an early warning to potentialinstability of the tar and cracking severity can be reduced bydecreasing the furnace outlet temperature (FOT).

FIG. 10 shows a correlation of FOT versus PV. Increasing the FOT willreduce the PV value up to instability (i.e., PV=1.0). With theappropriate treatment, the PV will remain higher (i.e., stable) at thesame temperature. Also note that the slope between the treated anduntreated curves is different, with the treated curve having a muchgentler slope. This provides more security and flexibility to theconversion enhancement objectives as the treatment acts as a buffer tothe rate of PV change with FOT. Accordingly, FIG. 10 is the correlationof the Furnace Outlet Temperature versus Pv showing that by increasingFOT the Pv will reduce up to instability, and with treatment, the Pvwill be higher at the same temperature, but also the slope is differentindicating that we provide more security and flexibility to theconversion enhancement objectives. By comparison, other known treatmentsystems, such as those described in European Patent Nos. 0321424 B1 and0529397 B1 to Faina, et al., do not impact Pv in the manner described bythe present invention.

Comparing the difference in the VFM measurements from the tar in theinlet of the furnace to measurements in the outlet of the furnace givesa direct measure of the severity of the cracking. When the VFM measuresinhomogeneities in the outlet stream, action can be taken on the processside, specific to customer specifications. For example, the simplestaction to be implemented is reducing the cracking severity in order toreduce the fouling rate on the furnace, exchangers, columns bottoms orsoaker drum. This reduces the risk and rate of fouling deposits, but italso reduces the amount of light hydrocarbon stream produced, so itreduces the profitability of operations. This course of action isaccompanied with the feed of high temperature antifoulant chemistry atthe rate of approximately 100 ppm. In order to maintain the highestefficiency of conversion and therefore the highest profitability, thegoal is to increase the tar stability (increase the P-value) byreplacing the converted resins by high temperature dispersant at ahigher dose that is up to about 500 ppm of chemical is injected. Theeconomical optimum to provide maximum profitability to the refinery isdependant on the individual refinery operations and objectives and islikely on the order of about 300 ppm. The specific value is determinedwith the use of the VFM measurements and our quantitative statisticalmodels.

Our MRA models attempt to define a mathematical correlation between theoperational parameters such as—feed quality, cracking severity,conversion and the fouling rate of the subject exchanger or furnace. Bynormalizing the mathematical model, the fouling rate is isolated fromthe varying operational parameters and the real fouling rate can bedemonstrated and quantified. By developing a corrected model whichreflects the residuals between the predicted model and the actualmeasured parameter, statistical process control techniques may beapplied to quantify the performance of the chemicals applied to controlfouling in the visbreaker unit. Precise determination of the foulingpotential in this manner allows a refinery to start treating anopportunity crude and quickly reach an optimum set of operatingconditions without incurring fouling, or to quickly change furnaceconditions (i.e., temperature) in order to increase or decrease theamount of specific fractions in the product (i.e., distribution ofcomponents and/or composition of visbroken product) which may berequired for immediate production needs, while assuring that operationremains within a safe stability band. In addition to enhanced yield orthroughput, it provides enhanced flexibility with minimized risk.

The present invention is adapted to control chemical feed based on VFMmeasurements to maximize yield of light HC streams in Visbreakeroperations. The VFM can also give an estimate of tar stability, which isproportional to HFT measurements. The program of the present inventioncontrols chemical feed based on a predefined furnace outlet temperature,and uses predictive modeling to verify and predict performance based onVFM measurements. The chemical feed rate is then directly tied tocustomer driven performance measurements such as run length and/orconversion rate. High temperature dispersants can replace the convertedresins to maintain tar stability while increasing the cracking severity;or, the system may increase tar stability by maintaining constantcracking severity. Moreover, measuring the tar characteristics with theVFM before and after the furnace indicates the amount of particulatesproduced directly in the cracking process.

A process for establishing effective visbreaker treatment may besummarized as follows. First, the user clearly defines the problem to besolved. Next, a unit survey or blank test of visbreaker operations isperformed. Next, operational data obtained from the unit survey isanalyzed, and baseline performance parameters are defined. Next,performance goals are measured in accordance with mutually agreed uponproduction goals and requirements, and then an appropriate treatmentprocedure may be designed. Next, the treatment procedure is implemented,monitored and serviced, and finally performance reports and quantitybenefits may be provided.

As shown in FIG. 11, tar stability conversion occurs as asphaltenes aredisbursed in the continuous phase through the peptizing action ofaromatics and resins. It may also be noted from the illustration thatcracking modifies the equilibrium so that asphaltenes could causeprecipitation—low peptisation value.

Exemplary data recorded from a visbreaker conversion trial is shown inFIG. 12. As it is noted from FIG. 12, the circled regions representareas to stop chemical injection under the same operating conditions.

FIGS. 13-16 illustrate exemplary data obtained during conversionenhancement application. As it can be noted from the illustrated data,an overall +3% conversion increase was achieved. In FIG. 15, Thermoflo7R630 was injected before preheat: average 300 ppm. It has to be notedthat even a conversion increase by 1% in the treated charge has to beconsidered extremely satisfying in terms of profit.

FIG. 17 illustrates VFM data versus corrected skin temperature overtime, and FIG. 18 is a schematic diagram illustrating exemplaryvisbreaker process types.

The operation described above of path length sampling to develop ameasure of concentration of dispersed phase correlates well with aconventional HFT measure of hot filtered tar and may also be used with asuitable protocol to derive the classical peptization value Pv. Thisallows the VFM to be used to assess the quality of the visbreakerproduct and efficiently blend or produce various required fuel or otheroils. The classical procedure for measuring Pv, in use for decades,involves slowly adding graded amounts of pure n-cetane C₁₆H₃₄ to asequence of samples of the product, maintaining each diluted sample in aheated bath for a time (e.g. thirty minutes) to allow the asphaltenes toagglomerate, and then detecting the concentration of tar. The differentsamples provide a graph of the product stability, with an abruptincrease in tar separation at the peptization value Pv. Theconcentration measured by the VFM of the present invention provides aneffective tool for performing such a Pv measurement quickly andrepeatably.

One suitable protocol substitute n-heptanes for cetane in the samplepreparation procedure, allowing the dilutions, heating and settling tobe performed quickly—on small samples, at lower temperature, and inshorter times. A classical P value is expressed as 1+Xmin, where Xmin isthe maximum dilution before flocculation occurs expressed in number ofmilliliters of diluent n-cetane per gram of sample. For use with the VFMof the present invention, using n-heptane as the diluent, the sequenceof samples with successively increasing dilution may be heated in awater bath at 100° C. for fifteen minutes, allowed to cool and stand forfifteen minutes, and then measured with the VFM. This substantiallyreduces the sample preparation time, and because the VFM requires only asmall path sampling procedure, the entire array of samples may be placedon a single slide—for example, a 9-well microsample plate, for theconcentration detection step, so measurement is simplified, and madequantifiable and repeatable. Because of the lower molecular weight ofthe lighter heptane diluent, a correction factor 1/0.443 is applied tothe diluent volume Xmin to correct for the different molecular weight ofcetane, so that the resulting P value is identical in value to theclassical measurement. A series of samples can be placed on the stage.Each sample comprises a small amount of aliphatic hydrocarbon (i.e.,n-cetane, n-heptane, etc.). The more aliphatic compound that needs to beadded, the more stable the tar. The light transmission is then measuredover a scan path on each individual sample. This allows a functionalcomparison to be made of optical density to the amount of aliphaticadded to each sample.

FIG. 19A illustrates the derived Pv obtained by this procedure for fivesamples of visbreaker fluid, compared to the P values determined by theclassical n-cetane laboratory testing analysis of the samples. Themeasurements are essentially identical. FIG. 19B graphs the VFMconcentration measurement (in arbitrary units) illustrating the onset ofinstability and flocculation. The value Pv is readily visible as thepoint at which there is a rapid increase in sample opacity with arelatively small increase in the amount of the aliphatic (heptane)diluent. This abrupt change in the VFM concentration measurement amongthe tested samples, may be automatically defined as an output with astraightforward software comparison algorithm to provide thismeasurement of product quality or fluid stability. Other aspects of thesample preparation such as the preparation of a set of differentdilutions and loading onto a microsample array for concentrationmeasurement may be fully automated, using various injection, handlingand transfer mechanisms that will be familiar from similar tasksperformed by equipment used to automate the handling, processing andanalysis of chemical, biological, medical or genetic sequencingmaterials.

While the disclosure has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present disclosure. As such,further modifications and equivalents of the disclosure herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the scope and spirit of the disclosure as defined by thefollowing claims.

1. A method to improve the yield or quality of light streams in avisbreaker unit, comprising the steps of: estimating a concentration ofinhomogeneities contained within a tar byproduct of visbreakeroperations; determining a fouling potential based on said concentration;determining an acceptable baseline parameter of tar stability based onsaid fouling potential; comparing said baseline parameter to theconcentration of inhomogeneities measured during subsequent visbreakeroperations; and regulating input of anti-fouling material into saidvisbreaker unit during running of visbreaker operations based on saidcomparison so as to achieve said improved yield or quality.
 2. Themethod of claim 1, wherein said regulating step includes selecting andcontrolling the type or quantity of said anti-fouling material beinginput into said visbreaker unit.
 3. The method of claim 2, furthercomprising the step of increasing a run length or conversion rate ofsaid visbreaker unit.
 4. The method of claim 3, further comprising thestep of estimating stability of said tar byproduct based on hotfilterable solids (HFT) measurements.
 5. The method of claim 1, whereinsaid regulating step is further based on a predetermined furnace outlettemperature.
 6. The method of claim 1, further comprising the step ofgenerating a predictive model to verify and predict performance of saidvisbreaker unit.
 7. The method of claim 1, further comprising the stepof replacing converted resins with high temperature dispersants toeither maintain tar stability while increasing cracking severity orincreasing tar stability while maintaining constant cracking severity.8. The method of claim 1, further comprising the steps of comparing VFMmeasurements at the inlet of the furnace and the outlet of the furnace,and using said comparison to indicate an amount of inhomogeneitiesproduced directly in the cracking process.
 9. The method of claim 1,further comprising the step of utilizing a chemistry of saidanti-fouling material to reduce the sensitivity of temperature on PV ofsaid tar byproduct and increase PV of said tar byproduct at a giventemperature compared with the PV of untreated tar in said visbreakerunit.
 10. The method of claim 1, further comprising the step of changingthe furnace temperature to modify the composition of visbroken product.11. The method of claim 1, wherein the step of determining a foulingpotential includes determining the peptization value (PV).
 12. A systemto improve the yield of light streams in a visbreaker unit, comprising:means for estimating a concentration of inhomogeneities contained withina tar byproduct of visbreaker operations; means for determining afouling potential based on said concentration; means for determining anacceptable baseline parameter of tar stability based on said foulingpotential; means for comparing said baseline parameter to theconcentration of inhomogeneities measured during subsequent visbreakeroperations; and means for regulating input of anti-fouling material intosaid visbreaker unit during running of visbreaker operations based onsaid comparison.
 13. The system of claim 12, wherein said means forestimating comprises: an optical lens system comprising a stage adaptedto receive a sample of said fluid; a light source for focusing a lightbeam onto said sample; means for directing said light beam along aplurality of path lengths within a predetermined area of said sample;means for detecting light transmitted through said sample along eachsaid path length; means for quantifying an intensity of said transmittedlight; and means for correlating said quantified transmitted light to aconcentration of said inhomogeneities in said sample.
 14. The system ofclaim 12, further comprising means for determining the type or quantityof said anti-fouling material being input into said visbreaker unit. 15.The system of claim 12, further comprising means for increasing a runlength or conversion rate of said visbreaker unit.
 16. The system ofclaim 12, further comprising means for estimating stability of said tarbyproduct based on hot filterable solids (HFT) measurements.
 17. Thesystem of claim 12, further comprising means for generating a predictivemodel to verify and predict performance of said visbreaker unit.
 18. Thesystem of claim 12, further comprising means for replacing convertedresins with high temperature dispersants to either maintain tarstability while increasing cracking severity or increasing tar stabilitywhile maintaining constant cracking severity.
 19. The system of claim12, further comprising means for comparing VFM measurements at the inletof the furnace and the outlet of the furnace, and means for using saidcomparison to indicate an amount of inhomogeneities produced directly inthe cracking process.
 20. The system of claim 12, further comprisingmeans for changing the furnace temperature to modify the composition ofvisbroken product.
 21. The system of claim 12, further comprising meansfor utilizing a chemistry of said anti-fouling material to reduce thesensitivity of temperature on PV of said tar byproduct and increasing PVof said tar byproduct at a given temperature compared with the PV ofuntreated tar in said visbreaker unit.
 22. The system of claim 12,wherein the means for determining a fouling potential determines PV ofsaid tar byproduct.
 23. The system of claim 12, wherein said stage isadapted to receive multiple samples comprising aliphatic compounds, saidsystem further comprising means for characterizing said concentration asa function of an amount of said aliphatic compounds so as to calculate apeptization value (PV) of said samples.